This study is the first report on the generation and use of 4-quinoiodonium as a Michael type acceptor for organic synthesis. In this paper, a new strategy has been established for the synthesis of an unusual iododiarylsulfone via the electrochemical oxidation of p-iodophenol as a model compound in the presence of p-toluenesulfinic acid (as a model nucleophile), under metal- and reagent-free conditions in a simple undivided cell using the carbon electrodes, which can serve as a general method for the synthesis of new iododiarylsulfone under green conditions.